CN101684034A - Sealing glass powder, sealing glass ceramic powder and application - Google Patents
Sealing glass powder, sealing glass ceramic powder and application Download PDFInfo
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- CN101684034A CN101684034A CN200810223367A CN200810223367A CN101684034A CN 101684034 A CN101684034 A CN 101684034A CN 200810223367 A CN200810223367 A CN 200810223367A CN 200810223367 A CN200810223367 A CN 200810223367A CN 101684034 A CN101684034 A CN 101684034A
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Abstract
The invention provides sealing glass powder, which is prepared from glass containing 20 to 40 mol percent of SiO2, 10 to 30 mol percent of B2O3, 10 to 40 mol percent of BaO, 2 to 15 mol percent of MgO, 0.1 to 5 mol percent of La2O3, 2 to 10 mol percent of Y2O3, 1 to 5 mol percent of ZrO, 0 to 15 mol percent of SrO and 0 to 30 mol percent of CaO. The invention also provides a method for forming sealing glass by sintering the glass powder. In addition, the invention provides glass ceramic powder and the method for forming the sealing glass ceramic by sintering the powder. Furthermore, the invention provides the application of the sealing glass and the sealing glass ceramic. The glass powder and the glass ceramic powder in the invention are simple in adopted raw materials and manufacturing process, low in cost and good in wetting quality and compatibility with connected parts and have the advantages of adjustable thermal expansion coefficient and good thermal stability.
Description
Technical field
The sealing glass that the present invention relates to a kind of sealing glass powder and form by this powder sintering, the sealing glass pottery that also relates to a kind of sealing glass ceramic powder and formed by this glass-ceramic powder sintering the invention still further relates to the method that realizes sealing-in with described sealing glass powder and sealing glass ceramic powder.
Background technology
Fuel cell has that effciency of energy transfer height, fuel range of choice are wide, easy to operate, environmental friendliness, advantage such as durable in use, is applicable to the structure of power station and even portable power supply, is the green energy resource of generally acknowledging.Solid Oxide Fuel Cell (SOFC) has board-like and two kinds of structures of tubular type, and board-like SOFC has advantages such as power density height, preparation technology is simple, preparation cost is low, and the board-like SOFC of middle temperature (600-800 ℃) is the focus of current domestic and international SOFC research.The sealing of board-like SOFC is not settled properly so far, and sealing material can't satisfy the requirement of SOFC operation steady in a long-term.Current, sealing becomes one of major obstacle of board-like SOFC development.
Sealing method of the prior art mainly contains means of press seals and seals two kinds firmly.Means of press seals need additionally be exerted pressure, and has increased fuel cell and has built the difficulty of heap, and had the more high shortcoming of leak rate; Hard sealing also needs further to solve problems such as the chemical compatibility, thermostability, thermal stress resistance of sealing material.The glass that forms by glass powder, glass-ceramic powder preparing that the present invention relates to, the scope that glass ceramic material belongs to hard sealing.
It is low that glass powder and glass-ceramic powder have a cost; sealing-in easily; be easy to advantages such as large-scale production; it is the SOFC seal, sealing materials of domestic and international broad research and employing; carried out comparatively extensive studies, as CN1469497A; CN1234617A; CN1414646A; CN1494176A; CN1649186A; CN1465647A; CN1469497; CN1746252A; CN1812159A; CN101075665A; US6475938; US6291092; US6541146; US5453331 etc. disclose a series of glass that formed by glass powder and glass-ceramic powder preparing; glass-ceramic seal materials.These researchs mainly concentrate on glass and the chemical stability of glass-ceramic seal materials under oxidation and reducing atmosphere, and and other component materials of SOFC between the matching and the aspects such as viscosity under service temperature of thermal expansivity.The related sealing material of above patent all fails to solve problems such as thermostability, consistency, matched coefficients of thermal expansion fully, and these factors have seriously limited the work-ing life (work-ing life of SOFC sealing material is mainly by two control indexes: parallel-adder settle-out time and times of thermal cycle) of sealing material.Disclose " in a kind of warm sealing glass and be used for the method for solid oxide fuel cell seal " literary composition in publication number is the Chinese patent application of CN100376046C, the molar content of contained component and each component is in the glass in the literary composition: SiO
220%-40%, B
2O35%-40%, BaO18.6%-41.6%, La
2O
30-11%, Y
2O
30-10%, ZrO0-30%, the glass that the experiment proved that this kind composition easily with SOFC in the utmost point material etc. of being connected react, make sealing glass lose stopping property.
The nearly stage, pottery reinforcing glass matrix material becomes the research focus of SOFC sealing material, this kind material can significantly improve the mechanical property of sealing material, but needs to solve the key issue of glassy phase and ceramic phase consistency (physical compatibility, chemical compatible).The article " Glass composite seals for SOFC application " of " Europe pottery " 2007 27 phase 1817-1822 of magazine page or leaf discloses NAS glass/MgO material, and the article of 2006 9 phase 12-15 of " fuel cell wall bulletin " magazine page or leaf " Joining properties of a composite glass-ceramic sealant " discloses BCS glass/ZrO
2Material, the article of 2007 170 phase 395-400 of " power technology " magazine page or leaf " Novel alkalineearth silicate sealing glass for SOFC Part II.Sealing and interfacialmicrostructure " discloses the material of Sr-Ca-Ni-Y-B silicate glass/NiO.The exploitation of pottery reinforcing glass sealing material makes the SOFC sealing material obtain further development, but still has heat-staple problem.Under the SOFC operating temperature, the reaction of glassy phase and ceramic phase causes the deterioration of critical natures such as these material coefficient of thermal expansion coefficients, thereby causes the inefficacy that seals, can not adapt to the long-time running of SOFC.Trace it to its cause, the mis-behave of ceramic reinforcing glass sealing material is because the composition of glass is reasonable inadequately, and incompatible between the stupalith.The character of glass is by the structures shape of glass, and the composition of glass has determined the structure of glass, thereby glass combination, the variation formed, even wherein the subtle change of a certain component concentration all can cause the change of glass property.Therefore need form glass and design,, make sealing material obtain good thermostability, chemical stability, can satisfy the requirement of SOFC long-time running to solve the chemical compatibility between glass and the pottery.
Summary of the invention
A purpose of the present invention provides a kind of sealing glass powder.
This another bright purpose provides a kind of sealing glass ceramic powder.
A further object of the present invention provides a kind of sealing glass.
A further object of the present invention provides a kind of sealing glass pottery.
A further object of the present invention provides a kind of sealing glass, and sealing glass is used for the sealing between metal, pottery, metal and the pottery.
A further object of the present invention provides a kind of sealing glass pottery, and the sealing glass-ceramic is used for the sealing between metal, pottery, metal and the pottery.
A further object of the present invention provides the described sealing glass powder of a kind of usefulness and realizes sealing the method for the treatment of the sealing-in thing.
A further object of the present invention provides the described sealing glass ceramic powder of a kind of usefulness and realizes sealing the method for the treatment of the sealing-in thing.
One aspect of the present invention provides a kind of sealing glass powder, and this powder is made by glass, and this glass comprises the SiO of 20-40mol%
2, 10-30mol% B
2O
3, 10-40mol% MgO, the La of 0.1-5mol% of BaO, 2-15mol%
2O
3, 2-10mol% Y
2O
3, 1-5mol% ZrO
2, the SrO of 0-15mol% and the CaO of 0-30mol%.In the prior art, the oxide compound that glass can be by forming glass or its carbonate etc. are fired and are formed.
The present invention provides a kind of sealing glass ceramic powder on the other hand, and this powder comprises glass powder and oxide powder, and described oxide powder is selected from 1) MgO, 2) ZrO
2With 3) use Y
2O
3Stable ZrO
2In one or more.
Preferably, described glass-ceramic powder comprises the sealing glass powder of 60-90vol% and the oxide powder of 10-40vol%.
Further aspect of the present invention provides a kind of sealing glass, and described sealing glass is used for 1) metal, 2) pottery or 3) sealing between metal and the pottery, wherein said sealing glass is made by described sealing glass powder.In the prior art, sealing glass is made by described sealing glass powder sintering.
Preferably, described sealing glass be used for Solid Oxide Fuel Cell 1) connect the utmost point, 2) electrode, 3) ionogen or 4) connect the sealing between the utmost point and the ionogen.
More preferably, the thermal expansivity of described sealing glass is 9.5-13.0*10
-6K
-1
Most preferably, described sealing glass is that 8-11 divides handkerchief second 650-800 ℃ viscosity.
Further aspect of the present invention provides a kind of sealing glass pottery, and described sealing glass pottery is used for 1) metal, 2) pottery or 3) sealing between metal and the pottery, wherein said sealing glass pottery is made by described sealing glass ceramic powder.In the prior art, the sealing glass pottery can form by the powder sintering of forming the sealing glass pottery.
Preferably, described sealing glass pottery be used for Solid Oxide Fuel Cell 1) connect the utmost point, 2) electrode, 3) ionogen or 4) connect the sealing between the utmost point and the ionogen.
More preferably, the thermal expansivity of described sealing glass pottery is at 9.5-13.0*10
-6K
-1Between.
Most preferably, described sealing glass pottery is that 8-11 divides handkerchief second 650-800 ℃ viscosity.
Further aspect of the present invention provides the described sealing glass powder of a kind of usefulness to realize sealing the method for the treatment of the sealing-in thing, and the described sealing-in thing for the treatment of is 1) metal, 2) pottery or 3) metal and pottery.
Preferably, this method may further comprise the steps:
A. at first under 80-100 ℃,, form mixture slurry with described sealing glass powder, fluidizer and dispersant, and mixture slurry injected mould, cooling and demolding obtains the glass biscuit, preferably, described fluidizer is a paraffin, and described dispersion agent is oleic acid or stearic acid;
B. the glass biscuit that step a is obtained is at 100-150 ℃, and insulation 15-45min obtains hardened glass biscuit;
C. hardened glass biscuit is placed and treat between the sealing-in thing, be heated to 700-800 ℃ with the speed of 3-7 ℃/min, insulation 2-5h, the speed with 3-7 ℃/min cools to 680-630 ℃ again, realizes treating the sealing between the sealing-in thing.
Further aspect of the present invention provides the described sealing glass ceramic powder of a kind of usefulness to realize sealing the method for the treatment of the sealing-in thing, and the described sealing-in thing for the treatment of is 1) metal, 2) pottery or 3) metal and pottery.
Preferably, this method may further comprise the steps:
A. under 80-100 ℃,, form mixture slurry with described sealing glass ceramic powder, fluidizer and dispersant, and mixture slurry injected mould, cooling and demolding obtains the glass-ceramic biscuit, preferably, described fluidizer is a paraffin, and described dispersion agent is oleic acid or stearic acid;
B. the glass-ceramic biscuit that step a is obtained is at 100-150 ℃, and insulation 45-75min obtains hardened glass-ceramic biscuit;
C. hardened glass-ceramic biscuit is placed and treat between the sealing-in thing, be heated to 800-1000 ℃ with the speed of 3-7 ℃/min, insulation 3-8h, the speed with 3-7 ℃/min cools to 850-750 ℃ again, realizes treating the sealing of sealing-in thing.
The character of sealing glass is by the structures shape of sealing glass, and the composition of glass has determined the structure of glass, thereby glass combination, the variation formed, even wherein the subtle change of a certain component concentration all can cause the change of glass property.Before this, the exploitation of SOFC sealing glass mainly concentrates on silicon (aluminium) silicate glass, and this type of glass is easy to crystallization or easy and contacted other thing phase reactions with it, and less stable has also just lost sealing function.Sealing glass powder among the present invention has increased MgO as the glass network modifier on the basis of existing sealing glass, no longer add ZnO and TiO
2, and optimize its content, its character is more stable.Why character is more stable, be because its glass network by [SiO
4] and [BO
4] tetrahedron forms the excellent in stability of this kind glass network jointly; Meanwhile, the polybase melange effect between the glass network modifier has also improved its stability, thereby this kind glass is not easy to separate out crystal, also be not easy and sealed object between react.In addition, sealing glass among the present invention also contains elements such as Mg, Y, Zr in forming, these elements can effectively suppress the reaction between glass and the described oxide powder, and the La element can promote the stable of thermal expansion coefficient of glass in the sealing glass among the present invention.The thermal expansivity of sealing glass is 9.5-13.0*10 among the present invention
-6K
-1The network structure of involved in the present invention this kind of sealing glass is very stable, crystallization activation energy is very high, and its character is highly stable under working conditions, and thermal treatment thousands of hours can crystallization, thermal expansivity is constant, and and sealed stupalith and metal between have good consistency.And this type of glass can be good infiltration SOFC by the sealing-in parts, as ionogen be connected the utmost point etc.
Contain the common dual network structure of forming of glassy phase and ceramic phase in the sealing glass pottery among the present invention, thereby they are except the characteristics with above-mentioned sealing glass, mechanical property also is greatly improved, and the ability of opposing thermal stresses also has significantly and strengthens.Simultaneously, the adjustability of ceramic phase component makes it to have realized: (a) thermal expansivity is adjustable, to guarantee the coupling of thermal expansivity; (b) viscosity is adjustable, guarantees that sealing material has suitable sealing temperature and use temperature, and sealing glass and sealing glass pottery are that 8-11 divides handkerchief second at 650-800 ℃ viscosity among the present invention.
Sealing glass among the present invention contains multiple different ingredients, and the composition and the thermal expansivity of part prescription see Table 1.
The prescription and the thermal expansivity thereof of table 1. part sealing glass
Glass-ceramic powder among the present invention is by above-mentioned glass powder (60vol%-90vol%) and MgO, ZrO
2, use Y
2O
3Stable ZrO
2(english abbreviation: one or more YSZ) are composited.The composition and the thermal expansivity of the part sealing glass ceramic formula among the present invention see Table 2.
The prescription and the thermal expansivity thereof of table 2. sealing glass pottery
Glass 3 and glass 6 respectively in the expression table 1. sequence number be 3 and 6 glass.
Beneficial effect of the present invention has fabulous thermostability for the sealing glass among the present invention, this glass 650 ℃, 700 ℃, 800 ℃ handle 1000-3000 hour after, no crystallization phenomenon, thermal expansivity is stablized; This glass be connected object good consistency arranged, under use temperature, do not have significantly reaction; The thermal expansivity of this glass and SOFC are good by sealing-in parts matching.The sealing glass pottery that is formed by the glass-ceramic powder preparing among the present invention has above advantage equally.
When glass powder and glass-ceramic powder were used for solid oxide fuel cell seal among the present invention, it was connected the utmost point (SS430) with SOFC, ionogen has good wetting property and consistency.
Sealing glass that glass powder and glass-ceramic powder preparing form among the present invention and sealing glass pottery have adjustable (9.5-13.0 * 10 of thermal expansivity
-6K
-1), can adapt to the demand at the different sealing-ins of SOFC position.
Sealing glass that glass and glass-ceramic powder preparing form among the present invention and glass-ceramic have the characteristics of Heat stability is good (1000-3000 hour).
Sealing glass that glass and glass-ceramic powder preparing form among the present invention and glass-ceramic have long service life (1000-3000 hour), can realize the characteristics of hundreds of thermal cyclings (200-500 time).
When realizing sealing-in by glass and glass-ceramic powder among the present invention, the moulding process of employing is compared with the ordinary hot casting die for improving hot die-casting method, has reduced the de-waxing process, has increased process of setting.
The raw material that sealing material adopted that the present invention prepares the Solid Oxide Fuel Cell use is simple, and manufacture craft is simple, and cost is low, is suitable for battery pile and uses.
Description of drawings
Below, describe embodiments of the invention in conjunction with the accompanying drawings in detail, wherein:
Fig. 1 be the embodiment of the invention 1 sealing glass, embodiment 2 and embodiment 3 sealing glass potteries work-ing life-leak rate figure.
Fig. 2 is the cycle index-leak rate figure of the embodiment of the invention 1 sealing glass, embodiment 2 and embodiment 3 sealing glass potteries.
Embodiment
Embodiment 1
(1) with 25mol%SiO
2, 22mol%B
2O
3, 20mol%BaO, 20mol%CaO, 6mol%MgO, 0.5mol%La
2O
3, 5mol%Y
2O
3, 1.5mol%ZrO
2Proportioning take by weighing each component, mix, place Platinum crucible.
(2) crucible that raw material is housed is placed retort furnace,, be cooled to 800 ℃ and take out shrend 1300 ℃ of insulations 4 hours, make glass material, again glass material is ground into the glass fragment, glass fragment ball milling is become the powder form, the particle diameter of powder is 50-60 μ m, oven dry.
(3) add 7.5g to 100 ℃ of heated paraffin, add the 92g glass powder, mix, add 0.5g oleic acid, mix and form the wax slurry.
(4) the wax slurry is injected mould, cooling, the demoulding, obtain the glass biscuit.
(5) the glass biscuit that step (4) is obtained makes it sclerosis at 130 ℃ of insulation 0.5h.
(6) place hardened glass biscuit fuel cell to connect between the utmost point (stainless steel SS430) and the battery sheet (pottery), be heated to 750 ℃ of insulation 3h with 5 ℃/min, cool to 650 ℃ of the use temperatures of this kind sealing glass material with 5 ℃/min, finish sealing-in between the connection utmost point and the battery sheet, the glass biscuit of this moment has formed sealing glass.
(7) sealing glass test in work-ing life, under use temperature, be incubated 3000h, leak rate is seen Fig. 1, as can be seen from the figure in whole test process, leak rate is lower than 0.001sccm/cm always, be far smaller than threshold value 0.09sccm/cm, illustrate that this kind sealing glass the work-ing life under service temperature can be above 3000 hours.
(8) thermal circulation performance test, thermal cycling mechanism is
Leak rate-cycle index graph of a relation is seen Fig. 2, and as can be seen from the figure this kind sealing glass still has excellent sealing performance after having passed through 500 thermal cyclings, that is, leak rate is far smaller than threshold value 0.09sccm/cm.
Embodiment 2
(1) with 25mol%SiO
2, 22mol%B
2O
3, 20mol%BaO, 10mol%SrO, 10mol%CaO, 6mol%MgO, 0.5mol%La
2O
3, 5mol%Y
2O
3, 1.5mol%ZrO
2Proportioning take by weighing each component, mix, place Platinum crucible.
(2) crucible that raw material is housed is placed retort furnace,, be cooled to 800 ℃ and take out shrend 1300 ℃ of insulations 3 hours, make glass material, again glass material is ground into the glass fragment, glass fragment ball milling is become glass powder, the particle diameter of glass powder is 90-100 μ m, oven dry.
(3) with the 80vol% glass powder, 10vol%MgO, 10vol% Y
2O
3Stable ZrO
2Proportioning take by weighing each component, mix, obtain the glass-ceramic powder.
(4) add 15.0g to 100 ℃ of heated paraffin, add 83.0g glass-ceramic powder, mix, add 1.0g oleic acid, 1.0g stearic acid, mix and form the wax slurry.
(5) the wax slurry is injected mould, cooling, the demoulding, obtain having the glass-ceramic biscuit.
(6) the glass-ceramic biscuit that step (5) is obtained makes it sclerosis 100 ℃ of insulations 45.
(7) place hardened glass-ceramic biscuit fuel cell to connect between the utmost point (stainless steel SS430), be heated to 800 ℃ of insulation 3h, cool to 750 ℃ of the use temperatures of this kind sealing glass pottery, finish and connect sealing-in between the utmost point with 3 ℃/min with 3 ℃/min.
(8) test in sealing glass pottery work-ing life, under use temperature, be incubated 2200h, leak rate is seen Fig. 1, as can be seen from the figure in whole test process, leak rate is lower than 0.001sccm/cm always, be far smaller than threshold value 0.09sccm/cm, illustrate that this kind sealing material the work-ing life under service temperature can be above 2200 hours.
(9) thermal circulation performance test, thermal cycling mechanism is
Leak rate-cycle index graph of a relation is seen Fig. 2, and as can be seen from the figure this kind sealing material still has excellent sealing performance after having passed through 250 thermal cyclings, that is, leak rate is far smaller than threshold value 0.09sccm/cm.
Embodiment 3
(1) with 23mol%SiO
2, 24mol%B
2O
3, 25mol%BaO, 15mol%CaO, 5mol%MgO, 1mol%La
2O
3, 5mol%Y
2O
3, 2mol%ZrO
2Proportioning take by weighing each component, mix, place Platinum crucible.
(2) crucible that raw material is housed is placed retort furnace,, be cooled to 800 ℃ and take out shrend, make glass material, again glass material is ground into the glass fragment, glass fragment ball milling is become glass powder, oven dry 1300 ℃ of insulations 5 hours.
(3) with 80vol% glass powder, 5vol%MgO, 5vol%ZrO
2, 10vol% Y
2O
3Stable ZrO
2Proportioning take by weighing each component, mix, obtain the glass-ceramic powder.
(4) add 10g to 80 ℃ of heated paraffin, add 88.5g glass-ceramic powder, mix, add 0.5g oleic acid, 1.0g stearic acid, mix and form the wax slurry.
(5) the wax slurry is injected mould, cooling, the demoulding, obtain the glass-ceramic biscuit.
(6) the glass-ceramic biscuit that step (5) is obtained makes it sclerosis at 130 ℃ of insulation 1h.
(7) place the sealing material biscuit fuel cell to connect between the utmost point (stainless steel SS430) and the battery sheet (pottery), be heated to 900 ℃ of insulation 5h with 5 ℃/min, cool to the use temperature (750 ℃) of this kind sealing glass pottery with 5 ℃/min, finish and connect sealing-in between the utmost point and the battery sheet.
(8) sealing glass pottery test in work-ing life, under use temperature, be incubated 1000h, leak rate is seen Fig. 1, as can be seen from the figure in whole test process, leak rate is lower than 0.00075sccm/cm always, be far smaller than threshold value 0.09sccm/cm, illustrate that this kind sealing material the work-ing life under service temperature can be above 1000 hours.
(9) thermal circulation performance test, thermal cycling mechanism is
Leak rate-cycle index graph of a relation is seen Fig. 2, and as can be seen from the figure this kind sealing material still has excellent sealing performance after having passed through 200 thermal cyclings, that is, leak rate is far smaller than threshold value 0.09sccm/cm.
Embodiment 4
(1) with 40mol%SiO
2, 10mol%B
2O
3, 10mol%BaO, 5mol%CaO, 15mol%MgO, 5mol%La
2O
3, 5mol%Y
2O
3, 5mol%ZrO
2And 5mol%SrO
2Proportioning take by weighing each component, mix, place Platinum crucible.
(2) crucible that raw material is housed is placed retort furnace,, be cooled to 800 ℃ and take out shrend 1300 ℃ of insulations 4 hours, make glass material, again glass material is ground into the glass fragment, glass fragment ball milling is become glass powder, the particle diameter of glass powder is 50-60 μ m, oven dry.
(3) add 7.5g to 100 ℃ of heated paraffin, add the 92g glass powder, mix, add 0.5g oleic acid, mix the formation mixture slurry.
(4) mixture slurry is injected mould, cooling, the demoulding, obtain the glass biscuit.
(5) the glass biscuit that step (4) is obtained makes it sclerosis at 100 ℃ of insulation 0.5h.
(6) hardened glass biscuit is placed between the battery sheet (pottery) of Solid Oxide Fuel Cell, be heated to 700 ℃ of insulation 2h with 3 ℃/min, cool to 630 ℃ of the use temperatures of this kind sealing material with 3 ℃/min, finish sealing-in between the battery sheet, the glass biscuit of this moment has formed sealing glass.
Embodiment 5
Present embodiment is identical with (2) with the step (1) of embodiment 4, and all the other steps are as follows:
(3) with the 90vol% glass powder, the proportioning of 10vol%MgO takes by weighing each component, mixes, and forms the glass-ceramic powder.
(4) add 10g to 100 ℃ of heated paraffin, add the glass-ceramic powder of 88.5g, mix, add 0.5g oleic acid, 1.0g stearic acid, mix and form the wax slurry.
(5) the wax slurry is injected mould, cooling, the demoulding, obtain the glass-ceramic biscuit.
(6) the glass-ceramic biscuit that step (5) is obtained makes it sclerosis at 150 ℃ of insulation 75min, obtains hardened glass-ceramic biscuit.
(7) hardened glass-ceramic biscuit is placed between the battery sheet (pottery) of Solid Oxide Fuel Cell, be heated to 1000 ℃ of insulation 8h with 7 ℃/min, cool to 850 ℃ of the use temperatures of this kind sealing material with 7 ℃/min, finish sealing-in between the battery sheet, the glass-ceramic biscuit of this moment has formed the sealing glass pottery.
Embodiment 6
Present embodiment is identical with (2) with the step (1) of embodiment 1, and all the other steps are as follows:
(3) add 7.5g to 80 ℃ of heated paraffin, add the 92g glass powder, mix, add 0.5g oleic acid, mix and form the wax slurry.
(4) the wax slurry is injected mould, cooling, the demoulding, obtain the glass biscuit.
(5) the glass biscuit that step (4) is obtained makes it sclerosis at 150 ℃ of insulation 45min.
(6) place hardened glass biscuit fuel cell to connect between the utmost point (stainless steel SS430) and the battery sheet (pottery), be heated to 800 ℃ of insulation 5h with 7 ℃/min, cool to 680 ℃ of the use temperatures of this kind sealing material with 7 ℃/min, finish sealing-in between the connection utmost point and the battery sheet, the glass biscuit of this moment has formed sealing glass.
Claims (11)
1. sealing glass powder, this powder is made by glass, and this glass comprises the SiO of 20-40mol%
2, 10-30mol% B
2O
3, 10-40mol% MgO, the La of 0.1-5mol% of BaO, 2-15mol%
2O
3, 2-10mol% Y
2O
3, 1-5mol% ZrO
2, the SrO of 0-15mol% and the CaO of 0-30mol%.
2. sealing glass ceramic powder, this powder comprises described sealing glass powder of claim 1 and oxide powder, and described oxide powder is selected from 1) MgO, 2) ZrO
2With 3) use Y
2O
3Stable ZrO
2In one or more.
3. sealing glass ceramic powder according to claim 2, wherein this powder comprises the sealing glass powder of 60-90vol% and the oxide powder of 10-40vol%l.
4. sealing glass, described sealing glass is used for 1) metal, 2) pottery or 3) sealing between metal and the pottery, it is characterized in that described sealing glass made by the described sealing glass powder of claim 1, preferably, described sealing glass be used for Solid Oxide Fuel Cell 1) connect the utmost point, 2) electrode, 3) ionogen or 4) connect the sealing between the utmost point and the ionogen, more preferably, the thermal expansivity of described sealing glass is 9.5-13.0*10
-6K
-1
5. sealing glass according to claim 4 is characterized in that described sealing glass is that 8-11 divides handkerchief second 650-800 ℃ viscosity.
6. sealing glass pottery, described sealing glass pottery is used for 1) metal, 2) pottery or 3) sealing between metal and the pottery, it is characterized in that described sealing glass pottery made by claim 2 or 3 described sealing glass ceramic powders, preferably, described sealing glass pottery be used for Solid Oxide Fuel Cell 1) connect the utmost point, 2) electrode, 3) ionogen or 4) connect the sealing between the utmost point and the ionogen, more preferably, the thermal expansivity of described sealing glass pottery is 9.5-13.0*10
-6K
-1
7. sealing glass pottery according to claim 6 is characterized in that described sealing glass pottery is that 8-11 divides handkerchief second 650-800 ℃ viscosity.
8. realize that with the described sealing glass powder of claim 1 sealing treats the method for sealing-in thing for one kind, the described sealing-in thing for the treatment of is 1) metal, 2) pottery or 3) metal and pottery.
9. method according to claim 8, this method may further comprise the steps:
A. at first under 80-100 ℃,, form mixture slurry with described sealing glass powder, fluidizer and dispersant, and mixture slurry injected mould, cooling and demolding obtains the glass biscuit, preferably, described fluidizer is a paraffin, and described dispersion agent is oleic acid or stearic acid;
B. the glass biscuit that step a is obtained is at 100-150 ℃, and insulation 15-45min obtains hardened glass biscuit;
C. hardened glass biscuit is placed and treat between the sealing-in thing, be heated to 700-800 ℃ with the speed of 3-7 ℃/min, insulation 2-5h, the speed with 3-7 ℃/min cools to 680-630 ℃ again, realizes treating the sealing between the sealing-in thing.
10. realize that with claim 2 or 3 described glass-ceramic powders sealing treats the method for sealing-in thing for one kind, the described sealing-in thing for the treatment of is 1) metal, 2) pottery or 3) metal and pottery.
11. method according to claim 10, this method may further comprise the steps:
A. under 80-100 ℃,, form mixture slurry with described glass-ceramic powder, fluidizer and dispersant, and mixture slurry injected mould, cooling and demolding obtains the glass-ceramic biscuit, preferably, described fluidizer is a paraffin, and described dispersion agent is oleic acid or stearic acid;
B. the glass-ceramic biscuit that step a is obtained is at 100-150 ℃, and insulation 45-75min obtains hardened glass-ceramic biscuit;
C. hardened glass-ceramic biscuit is placed and treat between the sealing-in thing, be heated to 800-1000 ℃ with the speed of 3-7 ℃/min, insulation 3-8h, the speed with 3-7 ℃/min cools to 850-750 ℃ again, realizes treating the sealing between the sealing-in thing.
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